Water → 2-Bromo-4-(9-bromo-2,3-dimethyl-naphtho[2,3-b]thiophen-4-yl)-6-cyclopentyl-phenol

HRID 1278819Notes

Reaction equation

HRID 1278819 reaction equation
[CH:1]1([C:6]2[CH:11]=[C:10]([C:12]3[C:24]4[C:23]([CH3:25])=[C:22]([CH3:26])[S:21][C:20]=4[C:19]([Br:27])=[C:18]4[C:13]=3[CH:14]=[CH:15][CH:16]=[CH:17]4)[CH:9]=[CH:8][C:7]=2[OH:28])[CH2:5][CH2:4][CH2:3][CH2:2]1.C([O-])(=O)C.[K+].[Br:34]Br.O>C(O)(=O)C>[Br:34][C:8]1[CH:9]=[C:10]([C:12]2[C:24]3[C:23]([CH3:25])=[C:22]([CH3:26])[S:21][C:20]=3[C:19]([Br:27])=[C:18]3[C:13]=2[CH:14]=[CH:15][CH:16]=[CH:17]3)[CH:11]=[C:6]([CH:1]2[CH2:2][CH2:3][CH2:4][CH2:5]2)[C:7]=1[OH:28]

Participants

6

Reactant 4

HCID 962WaterHCID 24408BromineHCID 517044Potassium AcetateHCID 184306982-Cyclopentyl-4-(9-bromo-2,3-dimethyl-naphtho[2,3-b]thiophen-4-yl)-phenol

Product 1

HCID 184307332-Bromo-4-(9-bromo-2,3-dimethyl-naphtho[2,3-b]thiophen-4-yl)-6-cyclopentyl-phenolYield 52%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent3×

Procedure

To a suspension of 2-cyclopentyl-4-(9-bromo-2,3-dimethyl-naphtho[2,3-b]thiophen-4-yl)-phenol (2.0 g, 4.4 mmol) and potassium acetate (4.4 g, 44.3 mmol) in glacial acetic acid (60 mL) was added dropwise over a period of 17 minutes a solution of bromine (0.27 mL, 5.3 mmol) in glacial acetic acid (8 mL). The thick reaction mixture was diluted with glacial acetic acid (20 mL). After stirring at room temperature for 2 h the reaction mixture was poured into water (500 mL). The solution was extracted once with diethyl ether (250 mL), and then with diethyl ether (100 mL). The combined extracts were washed twice with water (100 mL). Concentration under reduced pressure and chromatography with petroleum ether:ethyl acetate (98:2), followed by trituation with petroleum ether gave the title compound as a white solid (1.2 g, 52%): mp 189.5-191° C.; (DMSO-d6): δ 9.19 (s, 1H), 8.18 (d, 1H), 7.65-7.61 (m, 1H), 7.50-7.47 (m, 2H), 7.33 (d, 1H), 7.11 (d, 1H), 3.42 (quintet, 1H), 2.43 (s, 3H), 2.00-1.97 (m,2H ), 1.69-1.46 (m, 6H), 1.60 (s, 3H); MS(EI): [M+], 2 bromine isotope pattern, 528 (46%), 530 (100%), 532 (52%); Anal. Calc. for C25H22Br2OS: C, 56.62, H, 4.18, N, 0.00. Found: C, 55.78, H, 4.12, N, 0.05.

Workup

  1. extractionThe solution was extracted once with diethyl ether (250 mL)
  2. washThe combined extracts were washed twice with water (100 mL)
  3. concentrationConcentration under reduced pressure and chromatography with petroleum ether:ethyl acetate (98:2)

Sources & evidence

ORD record
ord-9d6ca2b009bd485a993207b385e253aa
Source dataset
uspto-grants-2002_09
Patent number
US06444670B2

Reaction notes

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